Ba
4GaN
3O
Takayuki Hashimoto and Hisanori Yamane*
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan
Correspondence e-mail: [email protected]
Received 24 April 2014; accepted 8 May 2014
Key indicators: single-crystal X-ray study;T= 293 K; mean(Ga–N) = 0.008 A˚;
Rfactor = 0.043;wRfactor = 0.099; data-to-parameter ratio = 22.2.
Red transparant platelet-shaped single crystals of tetrabarium gallium trinitride oxide, Ba4GaN3O, were synthesized by the Na flux method. The crystal structure is isotypic with Sr4GaN3O, containing isolated triangular [GaN3]
6
anionic groups. O2 atoms are inserted between the slabs of [Ba4GaN3]2+, in which the [GaN3]6 groups are surrounded by Ba2+atoms.
Related literature
For isotypic Sr4GaN3O, see: Mallinson et al. (2006). For the major phase in the product, Ba3Ga2N4, see: Yamane & DiSalvo (1996). For compounds containing isolated triangular-planar [GaN3]
6
nitridogallate anions, see: Parket al.(2003); Mallinsonet al.(2006); Hintze & Schnick (2010). For details of Madelung site potential and energy calculations, see: O’Keeffe (1992); Orhan et al.. (2002); Paszkowiczet al. (2004); Taylor (1984). For details of the synthetic procedure, see: Kowachet al.(1998).
Experimental
Crystal data
Ba4GaN3O
Mr= 677.11
Orthorhombic,Pbca a= 7.8130 (3) A˚
b= 25.6453 (10) A˚
c= 7.9162 (4) A˚
V= 1586.14 (12) A˚3
Z= 8
MoKradiation = 22.84 mm1
T= 293 K
0.180.130.07 mm
Data collection
Rigaku R-AXIS RAPID II diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999)
Tmin= 0.071,Tmax= 0.411
14273 measured reflections 1820 independent reflections 1588 reflections withI> 2(I)
Rint= 0.133
R[F2> 2(F2)] = 0.043
wR(F2) = 0.099
S= 1.05 1820 reflections
82 parameters
max= 2.54 e A˚ 3 min=1.72 e A˚ 3
Table 1
Selected geometric parameters (A˚ ,).
Ba1—N1i
2.675 (8)
Ba1—N1 2.799 (9)
Ba1—N2ii 2.998 (7) Ba1—O1iii 2.999 (8) Ba1—O1iv 3.054 (9) Ba2—O1v 2.683 (9) Ba2—N2v 2.687 (8) Ba2—N1iii 2.991 (9)
Ba2—N2 3.158 (8)
Ba2—O1 3.184 (9)
Ba2—O1vi
3.264 (10)
Ba3—N3vii 2.730 (7)
Ba3—N3i
2.762 (8)
Ba3—N3 2.764 (7)
Ba3—N1i 2.914 (9) Ba3—N3ii 2.994 (8) Ba4—N3ii 2.661 (8)
Ba4—N2 2.808 (7)
Ba4—N2v
2.862 (8)
Ba4—O1 3.133 (10)
Ba4—N1viii
3.231 (9)
Ga1—N3 1.876 (8)
Ga1—N2 1.908 (8)
Ga1—N1iii 1.924 (8)
N3—Ga1—N2 125.3 (3)
N3—Ga1—N1iii 119.8 (3)
N2—Ga1—N1iii
114.6 (4)
Symmetry codes: (i) xþ1 2;y;zþ
1
2; (ii) x;yþ 1 2;zþ
1
2; (iii) x;yþ 1 2;z
1 2; (iv) xþ1
2;yþ 1 2;z; (v)x
1 2;y;zþ
1 2; (vi)xþ
1 2;y;z
1 2; (vii)xþ
1 2;yþ
1 2;z; (viii)
xþ1 2;yþ
1 2;zþ1.
Data collection:RAPID-AUTO(Rigaku Corporation, 2005); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure:SHELXL97(Sheldrick, 2008); molecular graphics:VESTA(Momma & Izumi, 2008); software used to prepare material for publication:SHELXL97.
This work was supported in part by a Grant-in-Aid for Scientific Resarch (C) (No. 25420701, 2013) from the Ministry of Education, Culture, Sports and Technology (MEXT), Japan.
Supporting information for this paper is available from the IUCr electronic archives (Reference: HP2067).
References
Higashi, T. (1999).NUMABS. Rigaku Corporation, Tokyo, Japan. Hintze, F. & Schnick, W. (2010).Solid State Sci.12, 1368–1373.
Kowach, G. R., Lin, H. Y. & DiSalvo, F. J. (1998).J. Solid State Chem.141, 1–9. Mallinson, P. M., Ga´l, Z. A. & Clarke, S. J. (2006).Inorg. Chem.45, 419–423. Momma, K. & Izumi, F. (2008).J. Appl. Cryst.41, 653–658.
O’Keeffe, M. (1992).EUTAX. Arizona State University, USA.
Orhan, E., Jobic, S., Brec, R., Marchand, R. & Saillard, J.-Y. (2002).J. Mater. Chem.12, 2475–2479.
Park, D. G., Ga´l, Z. A. & DiSalvo, F. J. (2003).Inorg. Chem.42, 1779–1785. Paszkowicz, W., Podsiadło, S. & Minikayev, R. (2004).J. Alloys Compd,382,
100–106.
Rigaku Corporation (2005). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122. Taylor, D. (1984).Trans. Br. Ceram. Soc.83, 5–9.
Yamane, H. & DiSalvo, F. J. (1996).Acta Cryst.C52, 760–761. Structure Reports
Online
supporting information
Acta Cryst. (2014). E70, i28 [doi:10.1107/S1600536814010472]
Ba4GaN3O
Takayuki Hashimoto and Hisanori Yamane
S1. Comment
Ba4GaN3O is isostructural with Sr4GaN3O (Mallinson et al., 2006) which crystallizes in an orthorhombic cell with the
space group Pbca (No. 61). The coordination environment around Ga1 site and Ba1–Ba3 sites are shown in Fig.1. Ga1
atom is bonded to N1, N2 and N3 atoms and form a triangular anionic group of [GaN3]6-. Ga—N bond lengths of
1.876 (8)–1.924 (8)Å are comparable with those observed in [GaN3]6- groups of Sr3GaN3 and Sr6GaN5 (1.938 Å, 1.895 Å,
Park et al., 2003), Sr4GaN3O (1.880–1.921 Å, Mallinson et al., 2006) and LiBa5GaN3F5 (1.896–1.945 Å, Hintze &
Schnick, 2010). Ba1 atom is coordinated by two N1, one N2 and three O1 atoms, and Ba2 atom is by one N1, two N2 and
three O1 atoms. N1 and N2 atoms are in seven-fold coordination sites of one Ga and six Ba atoms, and N3 atom is in the
six-fold coordination site of one Ga and five Ba atoms. O1 atom is coordinated by seven Ba atoms. As shown in Fig. 2,
O1 atoms are situated at the sites between [Ba4GaN3] slabs which are composed of triangular [GaN3] groups and Ba
atoms in the a–c plane.
Mallinson et al., (2006) calculated Madelung site potential and Madelung energy per formula of Sr4GaN3O for four
models of O and N atom arrangement. They concluded the model with O atom located at the O1 site coordinated by only
Sr atoms is the most stable structure because this model showed the smallest deviation of the site potentials in atom sites
of the same species and the lowest energy. The site potentials and energy calculated by using EUTAX (O′Keeffe, 1992)
and VESTA (Momma & Izumi, 2008) programs with the data of the present study are -17.12 – -17.87 V for Ba1–Ba4,
-36.17 V for Ga1, 28.24 – 29.45 V for N1–N3, 16.86 V for O1, and -26,100 kJ/mol for Ba4GaN3O. The values of Ga, N
and O sites were consistent with the site potentials reported for Sr4GaN3O (Ga: -35.01 V, N: 29.58 – 31.38 V, O: 17.36 V)
(Mallinson et al., 2006). The difference between the Madelung energy per formula of Ba4GaN3O and the sum of
Madelung energies of Ba3N2 derived by the theoretical calculation (-12,200 kJ/mol, Orhan et al., 2002), BaO (-3,500
kJ/mol, Taylor, 1984) and GaN (-10,500 kJ/mol, Paszkowicz et al., 2004) calculated from the crystal structure data is
0.4%.
S2. Experimental
Starting materials were pieces of Ba (Sigma-Aldrich, 99.99%), Ga (Rasa Industries, 99.99995%) and Na (Nippon Soda
Co. Ltd., 99.95%), and powders of Si (Kojundo Chemical Laboratory, 99.999%) and NaN3 (Toyo Kasei Kogyo Co. Ltd.,
99.9%). In an Ar gas-filled glove box (O2 < 1 ppm, H2O < 1 ppm), Ba (1.00 mmol), Ga (0.25 mmol), Na (2.4 mmol), Si
(0.50 mmol) and NaN3 (1.2 mmol) were weighed and placed in a BN crucible (Showa Denko, 99.5%). The crucible was
sealed in a stainless-steel tube. The sample was heated to 750°C in an electric furnace with a rate of 6°C min-1. This
temperature was maintained for 2 hours and lowered to 550°C with a cooling rate of -2.8°C min-1. After that the sample
was cooled to room temperature by shutting off the electric power to the furnace. The stainless-steel tube was cut and
opened in the glove box, and the crucible was washed with liquid NH3 (Japan Fine Products, >99.999%) to dissolve away
was yellow transparent granular single crystals of Ba3Ga2N4 (Yamane & DiSalvo, 1996). A small amount of red
transparent platelet single crystals of Ba4GaN3O were included in the product.
Semi-quantitative elemental analysis of the red single crystals was carried out with an energy-dispersive X-ray detector
(EDX, EDAX, Genesis) attached to a scanning electron microscope (SEM, Hitachi, S-4800). Ba:Ga molar ratio
determined by the EDX analysis was 78:22 which was close to the ratio (4:1) of Ba4GaN3O. The oxygen was probably
originated from the surface oxide layers of the starting materials. Since Ba4GaN3O is unstable in air, a single crystal was
picked up from the product and sealed in glass capillaries in the glove box for XRD data collection.
The peaks of 2.25–2.54 e Å-3 in the Fo–Fc map were observed at 0.88–0.96 Å distant from Ba1–Ba3 atoms. These large
[image:3.610.119.490.227.593.2]differences are probably a result of the cut-off effect of the Fourier synthesis.
Figure 1
The atomic arrangement around Ba and Ga atoms in the structure of Ba4GaN3O. Displacement ellipsoids are drawn at
70% probability. Symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii) -x + 1/2, y + 1/2, z; (iii) x + 1/2, y, -z + 1/2; (iv) x + 1/2, -y +
Figure 2
Crystal structure of Ba4GaN3O illustrated with Ga-centered N atom triangles.
Tetrabarium gallium trinitride oxide
Crystal data Ba4GaN3O Mr = 677.11
Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 7.8130 (3) Å b = 25.6453 (10) Å c = 7.9162 (4) Å V = 1586.14 (12) Å3 Z = 8
F(000) = 2272 Dx = 5.671 Mg m−3
Mo Kα radiation, λ = 0.71075 Å Cell parameters from 11112 reflections θ = 3.0–27.5°
µ = 22.84 mm−1 T = 293 K Platelet, red
Rigaku R-AXIS RAPID II diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 10.0 pixels mm-1 ω scans
Absorption correction: numerical (NUMABS; Higashi, 1999) Tmin = 0.071, Tmax = 0.411
14273 measured reflections 1820 independent reflections 1588 reflections with I > 2σ(I) Rint = 0.133
θmax = 27.5°, θmin = 3.0° h = −9→10
k = −33→33 l = −10→10
Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.043 wR(F2) = 0.099 S = 1.05 1820 reflections 82 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
w = 1/[σ2(F
o2) + (0.P)2 + 18.6031P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001 Δρmax = 2.54 e Å−3 Δρmin = −1.72 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Ba1 0.36690 (8) 0.42906 (2) 0.32613 (7) 0.02148 (18)
Ba2 0.03129 (8) 0.06166 (2) 0.16149 (7) 0.02055 (18)
Ba3 0.45621 (7) 0.26486 (2) 0.23802 (7) 0.02003 (18)
Ba4 0.20527 (8) 0.15269 (2) 0.46083 (7) 0.02310 (19)
Ga1 0.20637 (12) 0.17178 (4) 0.01682 (12) 0.0157 (2)
N1 0.0710 (11) 0.3685 (3) 0.3614 (11) 0.0246 (19)
N2 0.3630 (10) 0.1319 (3) 0.1492 (9) 0.0187 (17)
N3 0.1943 (10) 0.2448 (3) 0.0124 (9) 0.0169 (17)
O1 0.2416 (12) 0.0314 (4) 0.4918 (11) 0.049 (2)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Ga1 0.0158 (5) 0.0183 (6) 0.0132 (5) −0.0002 (4) −0.0006 (4) −0.0001 (4)
N1 0.026 (4) 0.019 (5) 0.029 (5) 0.011 (4) −0.010 (4) 0.006 (3)
N2 0.022 (4) 0.020 (4) 0.015 (4) 0.006 (3) −0.002 (3) 0.000 (3)
N3 0.022 (4) 0.011 (4) 0.018 (4) −0.002 (3) −0.002 (3) −0.001 (3)
O1 0.053 (5) 0.052 (6) 0.041 (5) −0.007 (5) 0.001 (4) −0.010 (4)
Geometric parameters (Å, º)
Ba1—N1i 2.675 (8) Ba4—N1viii 3.231 (9)
Ba1—N1 2.799 (9) Ga1—N3 1.876 (8)
Ba1—N2ii 2.998 (7) Ga1—N2 1.908 (8)
Ba1—O1iii 2.999 (8) Ga1—N1iii 1.924 (8)
Ba1—O1iv 3.054 (9) Ga1—Ba3ix 3.2450 (11)
Ba1—Ga1ii 3.2466 (12) Ga1—Ba1iii 3.2467 (12)
Ba2—O1v 2.683 (9) Ga1—Ba3iii 3.3648 (11)
Ba2—N2v 2.687 (8) N1—Ga1ii 1.924 (8)
Ba2—N1iii 2.991 (9) N1—Ba1v 2.675 (8)
Ba2—N2 3.158 (8) N1—Ba3v 2.914 (9)
Ba2—O1 3.184 (9) N1—Ba2ii 2.991 (9)
Ba2—O1vi 3.264 (10) N1—Ba4x 3.231 (9)
Ba2—Ga1 3.3405 (12) N2—Ba2i 2.687 (8)
Ba3—N3vii 2.730 (7) N2—Ba4i 2.862 (8)
Ba3—N3i 2.762 (8) N2—Ba1iii 2.998 (7)
Ba3—N3 2.764 (7) N3—Ba4iii 2.661 (8)
Ba3—N1i 2.914 (9) N3—Ba3ix 2.730 (7)
Ba3—N3ii 2.994 (8) N3—Ba3v 2.762 (8)
Ba3—Ga1vii 3.2450 (11) N3—Ba3iii 2.994 (8)
Ba3—Ga1ii 3.3647 (11) O1—Ba2i 2.683 (9)
Ba4—N3ii 2.661 (8) O1—Ba1ii 2.999 (8)
Ba4—N2 2.808 (7) O1—Ba1xi 3.054 (9)
Ba4—N2v 2.862 (8) O1—Ba2xii 3.264 (10)
Ba4—O1 3.133 (10)
N1i—Ba1—N1 103.0 (3) Ba4iii—Ba3—Ba4viii 109.76 (2)
N1i—Ba1—N2ii 100.2 (2) Ga1i—Ba3—Ba4viii 75.61 (2)
N1—Ba1—N2ii 67.5 (2) N3vii—Ba3—Ba4i 44.25 (16)
N1i—Ba1—O1iii 84.3 (3) N3i—Ba3—Ba4i 79.12 (16)
N1—Ba1—O1iii 90.3 (2) N3—Ba3—Ba4i 88.33 (16)
N2ii—Ba1—O1iii 157.8 (2) N1i—Ba3—Ba4i 114.81 (15)
N1i—Ba1—O1iv 154.5 (3) N3ii—Ba3—Ba4i 125.84 (15)
N1—Ba1—O1iv 101.8 (3) Ga1vii—Ba3—Ba4i 79.26 (2)
N2ii—Ba1—O1iv 94.5 (2) Ga1ii—Ba3—Ba4i 158.61 (3)
O1iii—Ba1—O1iv 89.88 (12) Ga1—Ba3—Ba4i 64.48 (2)
N1i—Ba1—Ga1ii 91.49 (19) Ba4iii—Ba3—Ba4i 117.798 (17)
N1—Ba1—Ga1ii 36.16 (16) Ga1i—Ba3—Ba4i 56.77 (2)
N2ii—Ba1—Ga1ii 35.30 (15) Ba4viii—Ba3—Ba4i 115.14 (2)
O1iii—Ba1—Ga1ii 123.61 (19) N3ii—Ba4—N2 109.6 (2)
N1—Ba1—Ba2iv 135.83 (16) N3ii—Ba4—O1 166.3 (2)
N2ii—Ba1—Ba2iv 140.93 (15) N2—Ba4—O1 80.8 (2)
O1iii—Ba1—Ba2iv 56.82 (19) N2v—Ba4—O1 85.6 (2)
O1iv—Ba1—Ba2iv 54.92 (18) N3ii—Ba4—N1viii 97.3 (2)
Ga1ii—Ba1—Ba2iv 166.34 (3) N2—Ba4—N1viii 87.9 (2)
N1i—Ba1—Ba2ii 148.09 (19) N2v—Ba4—N1viii 158.0 (2)
N1—Ba1—Ba2ii 52.06 (18) O1—Ba4—N1viii 73.7 (2)
N2ii—Ba1—Ba2ii 54.58 (15) N3ii—Ba4—Ga1 90.91 (16)
O1iii—Ba1—Ba2ii 112.10 (18) N2—Ba4—Ga1 32.35 (15)
O1iv—Ba1—Ba2ii 56.35 (18) N2v—Ba4—Ga1 74.12 (15)
Ga1ii—Ba1—Ba2ii 56.61 (2) O1—Ba4—Ga1 102.37 (15)
Ba2iv—Ba1—Ba2ii 109.870 (18) N1viii—Ba4—Ga1 116.90 (14)
N1i—Ba1—Ba4viii 60.51 (19) N3ii—Ba4—Ba2i 134.97 (17)
N1—Ba1—Ba4viii 103.06 (16) N2—Ba4—Ba2i 47.79 (16)
N2ii—Ba1—Ba4viii 48.37 (15) N2v—Ba4—Ba2i 117.38 (16)
O1iii—Ba1—Ba4viii 144.23 (18) O1—Ba4—Ba2i 46.44 (17)
O1iv—Ba1—Ba4viii 118.70 (17) N1viii—Ba4—Ba2i 51.70 (15)
Ga1ii—Ba1—Ba4viii 67.67 (2) Ga1—Ba4—Ba2i 79.68 (2)
Ba2iv—Ba1—Ba4viii 120.92 (2) N3ii—Ba4—Ba2 136.94 (16)
Ba2ii—Ba1—Ba4viii 102.089 (19) N2—Ba4—Ba2 57.57 (17)
N1i—Ba1—Ba4iii 56.90 (19) N2v—Ba4—Ba2 47.55 (15)
N1—Ba1—Ba4iii 59.59 (18) O1—Ba4—Ba2 56.00 (16)
N2ii—Ba1—Ba4iii 111.04 (15) N1viii—Ba4—Ba2 120.82 (16)
O1iii—Ba1—Ba4iii 53.45 (19) Ga1—Ba4—Ba2 55.77 (2)
O1iv—Ba1—Ba4iii 135.30 (17) Ba2i—Ba4—Ba2 70.604 (15)
Ga1ii—Ba1—Ba4iii 77.60 (2) N3ii—Ba4—Ba3ii 49.31 (16)
Ba2iv—Ba1—Ba4iii 108.003 (19) N2—Ba4—Ba3ii 113.90 (17)
Ba2ii—Ba1—Ba4iii 110.09 (2) N2v—Ba4—Ba3ii 142.97 (15)
Ba4viii—Ba1—Ba4iii 105.50 (2) O1—Ba4—Ba3ii 118.88 (16)
N1i—Ba1—Ba2vii 47.19 (19) N1viii—Ba4—Ba3ii 49.91 (15)
N1—Ba1—Ba2vii 112.78 (17) Ga1—Ba4—Ba3ii 121.19 (3)
N2ii—Ba1—Ba2vii 147.32 (16) Ba2i—Ba4—Ba3ii 99.15 (2)
O1iii—Ba1—Ba2vii 41.16 (18) Ba2—Ba4—Ba3ii 169.46 (2)
O1iv—Ba1—Ba2vii 116.36 (17) N3ii—Ba4—Ba3x 47.62 (16)
Ga1ii—Ba1—Ba2vii 127.49 (3) N2—Ba4—Ba3x 153.75 (16)
Ba2iv—Ba1—Ba2vii 63.146 (17) N2v—Ba4—Ba3x 79.21 (15)
Ba2ii—Ba1—Ba2vii 152.86 (2) O1—Ba4—Ba3x 124.02 (16)
Ba4viii—Ba1—Ba2vii 103.594 (19) N1viii—Ba4—Ba3x 106.15 (15)
Ba4iii—Ba1—Ba2vii 54.148 (15) Ga1—Ba4—Ba3x 123.74 (2)
N1i—Ba1—Ba1i 42.85 (19) Ba2i—Ba4—Ba3x 155.60 (2)
N1—Ba1—Ba1i 144.95 (17) Ba2—Ba4—Ba3x 126.28 (2)
N2ii—Ba1—Ba1i 105.14 (15) Ba3ii—Ba4—Ba3x 64.206 (12)
O1iii—Ba1—Ba1i 92.97 (19) N3ii—Ba4—Ba1x 117.25 (17)
O1iv—Ba1—Ba1i 113.06 (19) N2—Ba4—Ba1x 126.50 (17)
Ga1ii—Ba1—Ba1i 120.41 (2) N2v—Ba4—Ba1x 51.53 (15)
Ba2iv—Ba1—Ba1i 72.121 (14) O1—Ba4—Ba1x 58.44 (17)
Ba4viii—Ba1—Ba1i 57.460 (13) Ga1—Ba4—Ba1x 121.41 (2)
Ba4iii—Ba1—Ba1i 95.36 (2) Ba2i—Ba4—Ba1x 104.86 (2)
Ba2vii—Ba1—Ba1i 54.518 (17) Ba2—Ba4—Ba1x 70.646 (17)
O1v—Ba2—N2v 91.9 (3) Ba3ii—Ba4—Ba1x 115.65 (2)
O1v—Ba2—N1iii 84.3 (2) Ba3x—Ba4—Ba1x 70.370 (17)
N2v—Ba2—N1iii 95.3 (2) N3ii—Ba4—Ba1ii 116.11 (16)
O1v—Ba2—N2 147.5 (2) N2—Ba4—Ba1ii 114.79 (16)
N2v—Ba2—N2 92.1 (2) N2v—Ba4—Ba1ii 116.15 (16)
N1iii—Ba2—N2 63.2 (2) O1—Ba4—Ba1ii 50.26 (16)
O1v—Ba2—O1 137.4 (3) N1viii—Ba4—Ba1ii 43.92 (14)
N2v—Ba2—O1 87.6 (2) Ga1—Ba4—Ba1ii 146.26 (3)
N1iii—Ba2—O1 138.1 (2) Ba2i—Ba4—Ba1ii 67.004 (17)
N2—Ba2—O1 75.0 (2) Ba2—Ba4—Ba1ii 105.66 (2)
O1v—Ba2—O1vi 93.5 (3) Ba3ii—Ba4—Ba1ii 71.359 (18)
N2v—Ba2—O1vi 170.4 (2) Ba3x—Ba4—Ba1ii 89.987 (19)
N1iii—Ba2—O1vi 93.1 (2) Ba1x—Ba4—Ba1ii 65.465 (13)
N2—Ba2—O1vi 87.6 (2) N3—Ga1—N2 125.3 (3)
O1—Ba2—O1vi 83.07 (11) N3—Ga1—N1iii 119.8 (3)
O1v—Ba2—Ga1 115.78 (19) N2—Ga1—N1iii 114.6 (4)
N2v—Ba2—Ga1 79.89 (17) N3—Ga1—Ba3ix 57.2 (2)
N1iii—Ba2—Ga1 34.82 (15) N2—Ga1—Ba3ix 174.9 (2)
N2—Ba2—Ga1 34.00 (14) N1iii—Ga1—Ba3ix 62.6 (3)
O1—Ba2—Ga1 106.04 (17) N3—Ga1—Ba1iii 143.7 (2)
O1vi—Ba2—Ga1 104.74 (16) N2—Ga1—Ba1iii 65.2 (2)
O1v—Ba2—Ba4v 57.8 (2) N1iii—Ga1—Ba1iii 59.1 (3)
N2v—Ba2—Ba4v 50.72 (16) Ba3ix—Ga1—Ba1iii 110.03 (3)
N1iii—Ba2—Ba4v 57.98 (17) N3—Ga1—Ba2 146.1 (2)
N2—Ba2—Ba4v 101.71 (14) N2—Ga1—Ba2 67.8 (2)
O1—Ba2—Ba4v 138.28 (17) N1iii—Ga1—Ba2 62.6 (3)
O1vi—Ba2—Ba4v 138.65 (15) Ba3ix—Ga1—Ba2 112.94 (3)
Ga1—Ba2—Ba4v 69.40 (2) Ba1iii—Ga1—Ba2 69.15 (3)
O1v—Ba2—Ba4 143.6 (2) N3—Ga1—Ba3iii 62.3 (2)
N2v—Ba2—Ba4 51.81 (17) N2—Ga1—Ba3iii 104.3 (2)
N1iii—Ba2—Ba4 95.48 (15) N1iii—Ga1—Ba3iii 99.1 (3)
N2—Ba2—Ba4 48.63 (13) Ba3ix—Ga1—Ba3iii 72.53 (2)
O1—Ba2—Ba4 54.66 (17) Ba1iii—Ga1—Ba3iii 81.70 (3)
O1vi—Ba2—Ba4 122.74 (17) Ba2—Ga1—Ba3iii 150.54 (4)
Ga1—Ba2—Ba4 61.44 (2) N3—Ga1—Ba3 50.6 (2)
Ba4v—Ba2—Ba4 91.37 (2) N2—Ga1—Ba3 74.7 (2)
O1v—Ba2—Ba1xi 94.3 (2) N1iii—Ga1—Ba3 168.6 (3)
N2v—Ba2—Ba1xi 121.42 (16) Ba3ix—Ga1—Ba3 107.55 (3)
N1iii—Ba2—Ba1xi 143.29 (17) Ba1iii—Ga1—Ba3 123.58 (3)
N2—Ba2—Ba1xi 110.87 (14) Ba2—Ga1—Ba3 128.70 (3)
O1—Ba2—Ba1xi 51.72 (17) Ba3iii—Ga1—Ba3 71.31 (2)
O1vi—Ba2—Ba1xi 50.26 (15) N3—Ga1—Ba4 99.0 (2)
Ga1—Ba2—Ba1xi 143.49 (3) N2—Ga1—Ba4 51.9 (2)
Ba4v—Ba2—Ba1xi 147.07 (2) N1iii—Ga1—Ba4 123.9 (3)
N2v—Ba2—Ba1iii 134.13 (17) Ba2—Ga1—Ba4 62.79 (2)
N1iii—Ba2—Ba1iii 47.56 (17) Ba3iii—Ga1—Ba4 135.86 (3)
N2—Ba2—Ba1iii 50.68 (13) Ba3—Ga1—Ba4 66.74 (2)
O1—Ba2—Ba1iii 103.69 (17) N3—Ga1—Ba3v 47.9 (2)
O1vi—Ba2—Ba1iii 51.16 (15) N2—Ga1—Ba3v 113.7 (2)
Ga1—Ba2—Ba1iii 54.24 (2) N1iii—Ga1—Ba3v 113.4 (3)
Ba4v—Ba2—Ba1iii 105.36 (2) Ba3ix—Ga1—Ba3v 71.35 (2)
Ba4—Ba2—Ba1iii 99.30 (2) Ba1iii—Ga1—Ba3v 167.54 (4)
Ba1xi—Ba2—Ba1iii 99.012 (17) Ba2—Ga1—Ba3v 98.71 (3)
O1v—Ba2—Ba1ix 47.36 (18) Ba3iii—Ga1—Ba3v 110.13 (3)
N2v—Ba2—Ba1ix 109.56 (16) Ba3—Ga1—Ba3v 65.886 (19)
N1iii—Ba2—Ba1ix 41.01 (14) Ba4—Ga1—Ba3v 64.00 (2)
N2—Ba2—Ba1ix 101.32 (13) Ga1ii—N1—Ba1v 173.9 (5)
O1—Ba2—Ba1ix 162.69 (17) Ga1ii—N1—Ba1 84.7 (3)
O1vi—Ba2—Ba1ix 79.87 (15) Ba1v—N1—Ba1 96.6 (3)
Ga1—Ba2—Ba1ix 75.82 (2) Ga1ii—N1—Ba3v 81.5 (3)
Ba4v—Ba2—Ba1ix 58.845 (16) Ba1v—N1—Ba3v 101.3 (3)
Ba4—Ba2—Ba1ix 134.90 (2) Ba1—N1—Ba3v 137.2 (3)
Ba1xi—Ba2—Ba1ix 116.853 (17) Ga1ii—N1—Ba2ii 82.6 (3)
Ba1iii—Ba2—Ba1ix 62.918 (10) Ba1v—N1—Ba2ii 91.8 (2)
N3vii—Ba3—N3i 92.5 (2) Ba1—N1—Ba2ii 80.4 (2)
N3vii—Ba3—N3 91.05 (3) Ba3v—N1—Ba2ii 136.8 (3)
N3i—Ba3—N3 157.9 (3) Ga1ii—N1—Ba4x 96.7 (3)
N3vii—Ba3—N1i 71.2 (2) Ba1v—N1—Ba4x 79.2 (2)
N3i—Ba3—N1i 98.9 (2) Ba1—N1—Ba4x 150.1 (3)
N3—Ba3—N1i 102.9 (2) Ba3v—N1—Ba4x 72.1 (2)
N3vii—Ba3—N3ii 170.0 (3) Ba2ii—N1—Ba4x 70.32 (19)
N3i—Ba3—N3ii 85.75 (3) Ga1—N2—Ba2i 168.3 (4)
N3—Ba3—N3ii 87.0 (2) Ga1—N2—Ba4 95.7 (3)
N1i—Ba3—N3ii 118.8 (2) Ba2i—N2—Ba4 81.5 (2)
N3vii—Ba3—Ga1vii 35.28 (16) Ga1—N2—Ba4i 109.4 (3)
N3i—Ba3—Ga1vii 97.59 (15) Ba2i—N2—Ba4i 80.6 (2)
N3—Ba3—Ga1vii 97.89 (16) Ba4—N2—Ba4i 130.0 (3)
N1i—Ba3—Ga1vii 35.89 (15) Ga1—N2—Ba1iii 79.5 (2)
N3ii—Ba3—Ga1vii 154.71 (15) Ba2i—N2—Ba1iii 96.9 (2)
N3vii—Ba3—Ga1ii 156.30 (16) Ba4—N2—Ba1iii 148.5 (3)
N3i—Ba3—Ga1ii 90.65 (16) Ba4i—N2—Ba1iii 80.09 (19)
N3—Ba3—Ga1ii 94.83 (16) Ga1—N2—Ba2 78.2 (3)
N1i—Ba3—Ga1ii 85.14 (15) Ba2i—N2—Ba2 90.1 (2)
N3ii—Ba3—Ga1ii 33.68 (15) Ba4—N2—Ba2 73.80 (18)
Ga1vii—Ba3—Ga1ii 121.03 (4) Ba4i—N2—Ba2 151.9 (3)
N3vii—Ba3—Ga1 87.43 (16) Ba1iii—N2—Ba2 74.74 (18)
N3i—Ba3—Ga1 126.79 (16) Ga1—N3—Ba4iii 170.9 (4)
N3—Ba3—Ga1 31.61 (16) Ga1—N3—Ba3ix 87.5 (3)
N1i—Ba3—Ga1 130.55 (17) Ba4iii—N3—Ba3ix 90.0 (2)
N3ii—Ba3—Ga1 85.77 (15) Ga1—N3—Ba3v 101.9 (3)
Ga1ii—Ba3—Ga1 109.24 (3) Ba3ix—N3—Ba3v 94.4 (2)
N3vii—Ba3—Ba4iii 88.97 (16) Ga1—N3—Ba3 97.8 (3)
N3i—Ba3—Ba4iii 154.98 (16) Ba4iii—N3—Ba3 83.8 (2)
N3—Ba3—Ba4iii 46.89 (16) Ba3ix—N3—Ba3 172.1 (3)
N1i—Ba3—Ba4iii 58.03 (17) Ba3v—N3—Ba3 90.1 (2)
N3ii—Ba3—Ba4iii 96.78 (14) Ga1—N3—Ba3iii 84.1 (3)
Ga1vii—Ba3—Ba4iii 69.95 (2) Ba4iii—N3—Ba3iii 87.1 (2)
Ga1ii—Ba3—Ba4iii 78.55 (2) Ba3ix—N3—Ba3iii 86.1 (2)
Ga1—Ba3—Ba4iii 78.22 (2) Ba3v—N3—Ba3iii 174.0 (3)
N3vii—Ba3—Ga1i 87.80 (16) Ba3—N3—Ba3iii 88.8 (2)
N3i—Ba3—Ga1i 30.24 (16) Ba2i—O1—Ba1ii 91.5 (3)
N3—Ba3—Ga1i 128.27 (16) Ba2i—O1—Ba1xi 106.8 (3)
N1i—Ba3—Ga1i 125.19 (17) Ba1ii—O1—Ba1xi 139.5 (3)
N3ii—Ba3—Ga1i 85.74 (14) Ba2i—O1—Ba4 75.8 (2)
Ga1vii—Ba3—Ga1i 109.63 (3) Ba1ii—O1—Ba4 76.3 (2)
Ga1ii—Ba3—Ga1i 106.15 (2) Ba1xi—O1—Ba4 142.6 (3)
Ga1—Ba3—Ga1i 96.74 (3) Ba2i—O1—Ba2 89.6 (2)
Ba4iii—Ba3—Ga1i 174.14 (3) Ba1ii—O1—Ba2 144.2 (3)
N3vii—Ba3—Ba4viii 99.21 (16) Ba1xi—O1—Ba2 73.36 (19)
N3i—Ba3—Ba4viii 45.37 (16) Ba4—O1—Ba2 69.3 (2)
N3—Ba3—Ba4viii 154.63 (16) Ba2i—O1—Ba2xii 86.5 (3)
N1i—Ba3—Ba4viii 59.70 (17) Ba1ii—O1—Ba2xii 72.9 (2)
N3ii—Ba3—Ba4viii 86.56 (15) Ba1xi—O1—Ba2xii 72.5 (2)
Ga1vii—Ba3—Ba4viii 78.43 (2) Ba4—O1—Ba2xii 143.9 (3)
Ga1ii—Ba3—Ba4viii 67.05 (2) Ba2—O1—Ba2xii 142.8 (3)
Ga1—Ba3—Ba4viii 169.55 (3)
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1/2, y+1/2, z; (v) x−1/2, y, −z+1/2; (vi) −x+1/2, −y, z−1/2; (vii)
